Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
  • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
  • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
  • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
  • C07C311/21—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
  • C07C311/29—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring

Definitions

• the present invention relates to a silver halide color photographic material containing a coupler for forming a color photographic image and, more particularly, to a silver halide color photographic material containing a novel coupler for forming a yellow dye, and a method for producing yellow images using the same.
• a yellow dye image is obtained in the presence of the yellow coupler, which has excellent solubility, dispersion stability and spectral absorption characteristics, particularly, high color-forming rate, a high coloring density, excellent storage stability, and the coupling reactivity stable to pH change in the color developing solution which does not contain benzyl alcohol.
• a subtractive color process comprises reducing exposed silver halide grains by an aromatic primary amine type color developing agent to prepare an oxidation product of the color developing agent and coupling the oxidation product thereof with couplers which form yellow, cyan and magenta dyes in the silver halide emulsion to form color images.
• a yellow coupler for forming a yellow dye a compound having an active methylene group
• a magenta coupler for forming a magenta dye a compound of the pyrazolone type pyrazolone benzimidazole type, indazolone type and the like is used
• a cyan coupler for forming a cyan dye a compound of the phenol type and a compound of the naphthol type are used.
• Each coupler is dissolved in a water-insoluble organic solvent having a high boiling point, with an auxiliary solvent, if necessary, and is added to a silver halide emulsion, or each coupler is added into the emulsion as an aqueous alkaline solution.
• a water-insoluble organic solvent having a high boiling point with an auxiliary solvent, if necessary, and is added to a silver halide emulsion, or each coupler is added into the emulsion as an aqueous alkaline solution.
• the former case is preferable over the latter case in terms of light resistance, moisture resistance, heat resistance, granularity and color sharpness.
• Each coupler is substantially required to have properties such that the coupler not only forms a dye but also has high solubility for an organic solvent having a high boiling point or for an alkaline solution, high dispersibility and stability in a silver halide photographic emulsion.
• the thus formed dye should be fast to light, heat and moisture, its spectral absorption characteristic should be excellent, its transparency should be excellent, its images should be clear and sharp and, importantly, its coloring density and color forming rate should be high.
• skeleton structures of a yellow coupler include pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malonester monoamide type, benzothiazolyl acetate type, benzoxazolylacetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolyl acetate type couplers. Of these couplers, benzoylacetanilide type and pivaloylacetanilide type couplers are preferred.
• a yellow coupler of ⁇ -acylacetanilide containing an alkoxyalkylsulfonamide group at a non-coupling position is disclosed. It is further disclosed therein that an ether bond is introduced into a hydrophobic alkyl group part of an alkylsulfonamide group to increase the hydrophilic property, and that as a result thereof, the coupling activity of the yellow coupler is improved. However, ths thus formed dye does not have light fastness.
• Yellow couplers of ⁇ -amylacetanilide having an alkylsulfonamide group which is substituted by a predetermined substituent such as an alkylthio group, an alkyl sulfonyl group, an acyloxy group, an alkoxycarbonyl group, an amino group, a carbamoyl group, an imide group, a sulfonamide group and the like, are disclosed in Japanese Patent Application (OPI) No. 21738/83. These couplers also do not have light fastness. In addition, these couplers have a low coupling activity.
• Yellow couplers of ⁇ -acylacetanilide wherein a nitrogen atom in a sulfonamide group is substituted by a substituent, such as a cyano group, a halogen atom, an alkyl group, an aryl group or a heterocyclic group and the like, are disclosed in Japanese Patent Application (OPI) No. 121126/79.
• a substituent such as a cyano group, a halogen atom, an alkyl group, an aryl group or a heterocyclic group and the like.
• these couplers have a low coupling reactivity and the thus formed dye is not fast to light, heat, humidity and the like.
• Yellow couplers of ⁇ -acylacetanilide having a halogen atom or an alkyl group at the 2-position thereof having a halogen atom, an alkyl group or an alkoxyl group and having an alkylsulfonamide or an alkylsulfonamide substituted by a phenyl group are disclosed in Japanese Patent Application (OPI) No. 42046/83.
• these couplers have such a serious defect in that the thus formed dye has poor light fastness.
• Yellow couplers of ⁇ -pivalylacetanilide having at a coupling position an aryloxy group containing a carbonyl group, a sulfonyl group or a phosphenyl group at an ortho position of the oxygen atom thereof and an alkylsulfonamide group at the 5-position thereof are disclosed in U.S. Pat. No. 4,401,752.
• the thus formed dye of these couplers has poor light fastness.
• a first object of the present invention is to provide a novel yellow coupler having a satisfactory coupling activity when using a color developing solution having added thereto no benzyl alcohol and a method for preparing yellow dye images using the same.
• a second object of the present invention is to provide a novel yellow coupler which is stable to changes in the pH of a color developing solution and has reduced unevenness of color image density.
• a third object of the present invention is to provide a novel yellow coupler having excellent storage stability of the thus formed color images, that is, fastness to light, heat and moisture.
• a fourth object of the present invention is to provide a novel yellow coupler having high solubility to organic solvents having a high boiling point, good dispersibility and stability to a silver halide color photographic emulsion.
• a fifth object of the present invention is to provide a novel yellow coupler exhibiting satisfactory coupling activity even with the use of reduced amounts of organic solvents having a high boiling point and realizing therefore the reduction of the film thickness.
• a sixth object of the present invention is to provide a photographic light-sensitive material which can be processed at a high temperature and a high speed rate by using the novel yellow coupler.
• R 1 represents a substituted or unsubstituted tertiary alkyl or aryl group
• R 2 represents a chlorine atom or an alkoxy group
• R 3 represents a substituted or unsubstituted alkyl or aryl group
• R 4 represents a chlorine atom when R 1 represents a tertiary alkyl group
• R 4 represents a hydrogen atom or a chlorine atom when R 1 represents an aryl group.
• the tertiary alkyl groups represented by R 1 include unsubstituted (e.g., a t-butyl group) and substituted alkyl groups having from 4 to 8 carbon atoms.
• the substituents introduced into the above-described alkyl groups include halogen atoms (e.g., a fluorine atom, a chlorine atom, a bromine atom), alkoxy groups (e.g., a methoxy group, an ethoxy group), aryloxy groups (e.g., a phenoxy group, a 4-chlorophenoxy group), alkylthio groups (e.g., an n-butylthio group), arylthio groups (e.g., a phenylthio group), alkylsulfonyl groups (e.g., a methanesulfonyl group), arylsulfonyl groups (e.g., a benzen
• the aryl group represented by R 1 is preferably a phenyl group and may contain a substituent.
• the substituents of the above-described aryl group include those described above for the substituted alkyl groups and further include alkyl groups (e.g., a methyl group, an ethyl group, a t-butyl group).
• R 2 represents a chlorine atom or an alkoxy group having from 1 to 4 carbon atoms (e.g., a methoxy group, an ethoxy group).
• the alkyl group represented by R 3 includes an unsubstituted alkyl group having from 1 to 20 carbon atoms (e.g., an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, an n-hexadecyl group) or a substituted alkyl group.
• the substituents include an alkoxy group (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group, a 2-chlorophenoxy group), an aryl group (e.g., a phenyl group), an alkylthio group (e.g., a methylthio group), an arylthio group (e.g., a phenylthio group), a sulfonyl group (e.g., a methanesulfonyl group, a benzenesulfonyl group), an acyloxy group (e.g., an acetoxy group), an alkoxy- or aryloxycarbonyl group (e.g., an ethoxycarbonyl group), an amino group (e.g., a diethylamino group), an acylamino group (e.g., an acetamide group), a cyano group, and
• the aryl group represented by R 3 is preferably a phenyl group and may contain a substituent.
• the substituents of the aryl group contain those as described above for alkyl groups.
• the yellow coupler represented by formula (I) has such features that one hydrogen atom at an active position is substituted by a 4-cyanophenoxy group or a 2-chloro-4-cyanophenoxy group and that the ⁇ -acylacetanilide contains a chlorine atom or an alkoxy group at the 2-position thereof and an alkylsulfonamide group or an arylsulfonamide group at the 5-position thereof. Due to the above features it is believed that the yellow coupler of the present invention has faborable characteristics.
• Preferred couplers used in the present invention are represented by formula (II). ##STR3## wherein R 5 represents a substituted or unsubstituted tertiary alkyl group having from 4 to 8 carbon atoms, R 6 represents an unsubstituted alkyl group or an alkyl group substituted by an alkoxy group having from 6 to 20 carbon atoms and further represents groups shown by formulae (III), (IV) and (V).
• R 7 represents an unsubstituted alkyl group or an alkyl group substituted by an alkoxy group having from 1 to 12 carbon atoms and R 8 represents an unsubstituted alkyl group having from 1 to 8 carbon atoms; and R 2 has the same definition as that in formula (I).
• Couplers used in the present invention are represented by formula (VI). ##STR5## wherein R 9 is an unsubstituted alkyl group having from 6 to 16 carbon atoms.
• couplers used in the present invention are illustrated below, but the present invention is not construed as limited thereto.
• Novel couplers in accordance with formula (I) of the present invention can be prepared by reacting ⁇ -chloro- ⁇ -acylacetanilide represented by formula (VII) ##STR45## wherein R 1 to R 3 have the same definition as described above, with o-substituted p-cyanophenol represented by formula (VIII) ##STR46## wherein R 4 has the same definition as described above, in the presence of base if necessary.
• a reaction temperature ranges from 20° to 90° C., preferably 30° to 60° C.
• the molar ratio of ⁇ -chloro- ⁇ -acylacetanilide and p-cyanophenol is generally 1 to 5, preferably 1.5 to 3.
• Couplers represented by formula (VII) and couplers of the present invention represented by formula (I) can easily be synthesized in accordance with the methods disclosed in U.S. Pat. Nos. 3,265,506, 3,408,194, Japanese Patent Application (OPI) Nos. 99433/79 and 115219/77.
• p-Cyanophenol represented by formula (VIII) is a known compound and can be snythesized by chlorinating p-cyanophenol with sulfuryl chloride when R 4 is a chlorine atom, as disclosed in Beilstein, 10, 176.
• Two or more couplers of the present invention can be added to one layer and one type of coupler can be added to two or more layers, respectively.
• the couplers of the present invention can be used in combination with known pivaloylacetanilide type and benzoylacetanilide type couplers, such as nitrogen atom released type yellow couplers as disclosed in Japanese Patent Publication No. 10739/83, U.S. Pat. Nos. 4,401,752, 4,326,024, Research Disclosure, No. 18053 (April, 1979), British Pat. No. 1,425,020, German Patent Application (OLS) Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812, or oxygen atom released type yellow couplers as disclosed in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501 and 4,022,620.
• couplers of the present invention are used in combination with known couplers, it is preferred that couplers of the present invention are used in a high sensitive blue-sensitive emulsion layer and nitrogen atom released type yellow couplers are added to a low sensitive blue-sensitive emulsion layer.
• the couplers of the present invention are generally added in an amount of 2 ⁇ 10 -3 to 5 ⁇ 10 -1 mol, preferably 1 ⁇ 10 -2 to 5 ⁇ 10 -1 mol, per mol of silver in an emulsion.
• couplers of the present invention are used in combination with the above-described couplers, it is preferred that the total additive amounts of couplers which form the same color fall within the above ranges.
• the silver halide color photographic materials containing yellow couplers of the present invention have different silver halide compositions, additives and supports in accordance with their intended purpose, can be prepared in accordance with a conventional method (as described in Research Disclosure, No. 18716 (November, 1979) and ibid., No. 17643 (December, 1978) and can be used for both color negative films and color reversal films.
• the light-sensitive materials in accordance with the present invention can be developed by any conventional methods (as described in the above-mentioned references).
• the solution was introduced into 400 ml of an aqueous solution containing 3.5 g of sodium hydroxide and the reaction mixture was extracted with 500 ml of ethyl acetate.
• the oil layer was washed with water and made acidic with dilute hydrochloric acid and washed again with water.
• the oil layer was dried in the presence of magnesium sulfate and concentrated under reduced pressure to obtain 45 g of the residue.
• the residue was crystallized from a mixed solvent of 60 ml of ethyl acetate and 400 ml of n-hexane to obtain 40 g of white crystals. Melting Point: 114° to 118° C. These crystals were recrystallized from 50 ml of ethyl acetate and 100 ml of n-hexane to obtain 30.0 g of Coupler 6. Melting Point: 123° to 124° C.
• the solution was reacted for 3 hours at 30° to 40° C., and was added to 300 ml of an aqueous solution containing 2.1 g of sodium hydroxide. Then, the reaction mixture was extracted with 400 ml of ethyl acetate. The oil layer was washed with water, made acidic with dilute hydrochloric acid and was washed with water again.
• the oil layer was dried in the presence of magnesium sulfate and concentrated under reduced pressure to obtain 36 g of the residue.
• the residue was crystallized from ethyl acetate/n-hexane (volume ratio: 1/5, 200 ml ).
• the filtrated crystals were recrystallized from ethyl acetate/n-hexane (volume ratio: 1/8, 300 ml ) to obtain 25.5 g of Coupler 16. Melting Point: 119° to 120° C.
• a photographic element having layers composed of the following compositions on a cellulose acetate film support was prepared.
• a yellow coupler and tricresyl phosphate were mixed so that the weight mixing ratio was 3:1, 3 parts of ethyl acetate was added thereto and dissolved while being heated at 40° C.
• the resulting solution was dispersed and emulsified in 20 parts of a 3% aqueous gelatin solution containing 0.3% of a surface active agent (dodecylbenzene sodium sulfonate) to obtain an emulsified dispersion of the yellow coupler.
• the thus obtained emulsified dispersion and silver iodobromide emulsion (silver iodide: 6 mol %) were mixed to prepare a solution so that the molar ratio of silver to the coupler was 3.5:1.
• a 1.5% aqueous gelatin solution having mixed with 0.2% of a hardening agent (1,3-vinylsulfonyl-2-propanol) and 0.01% of a surface active agent (Triton X-200) was prepared.
• Photographic elements designated Sample Nos. 101 to 113 were prepared changing yellow couplers as used in the first layer to those as shown in Table 1. The amount of coupler coated was adjusted to 1.25 mmol/m 2 .
• samples wherein the weight ratio of yellow couplers and tricresyl phosphate was 10:1 were prepared (Sample Nos. 114 to 126).
• composition of the processing solutions used in each step was as follows.
• Couplers used for comparison ##STR47##
• the present invention exhibits a high gamma, a high sensitivity and a high color forming property (high color density) without increasing fog.
• Comparative Coupler (A) exhibited a comparatively high color forming property (high color density) when the ratio of tricresyl phosphate/coupler has high (Sample No. 108), and exhibited great low contrast and reduced sensitivity when the amount of tricresyl phosphate was reduced. On the other hand, it is apparent that the color forming property of the yellow 2-equivalent coupler of the present invention does not depend upon the amount of tricresyl phosphate employed.
• a photographic element having layers composed of the following compositions on a paper support on both surfaces of which were laminated with polyethylene was prepared.
• a yellow coupler and di-n-butylphthalate were mixed so that the weight mixing ratio was 8:1, 3 parts of ethyl acetate was added thereto and dissolved while being heated at 40° C.
• the resulting solution was dispersed and emulsified in a 3% aqueous gelatin solution containing 0.3% of a surface active agent (dodecylbenzene sodium sulfonate) to obtain an emulsified dispersion of yellow coupler.
• a solution was prepared wherein the thus obtained emulsified dispersion and silver chlorobromide emulsion (silver bromide: 80 mol %) were mixed so that the molar ratio of silver to coupler was 3.5:1.
• a 1.5% aqueous gelatin solution having mixed therewith 0.2% of a hardening agent (1,3-vinylsulfonyl-2-propanol) and 0.01% of a surface active agent (Triton X-200) was prepared.
• Photographic elements designated Sample Nos. 200 to 210 were prepared changing yellow couplers used in the first layer to those as shown in Table 2. The amount of coupler coated was adjusted to 1.0 mmol/m 2 .
• composition of the processing solutions used in each step was as follows.
• Color Developing Solution (B) had the same composition as that of Color Developing Solution (A) except that benzyl alcohol was removed.
• Sample No. 203 (Coupler 1) shows an excellent color forming property than Sample No. 201 (Comparative Coupler (B)) in Color Developing Solutions (A) and (B).
• a multilayered color light-sensitive material composed of layers having the following composition respectively on an undercoated cellulose triacetate film support was prepared and designated Sample No. 301.
• Second Red-sensitive Emulsion Layer Second Red-sensitive Emulsion Layer
• Second Protective Layer Thirteenth Layer: Second Protective Layer
• Gelatin Hardening Agent H-3 and a surface active agent were added in an amount as described in the second layer of Example 1.
• Sample Nos. 302 to 318 were prepared in the same manner as Sample No. 301 except for changing the coupler (C-1) used in the eleventh layer to those shown in Table 6.
• the thus prepared films were exposed through a wedge for a sensitometry to white light from a 4,800° K. light source. Then, the color images were obtained by reversal processing. The optical densilty of the yellow images among color images was measured through a blue filter. The results are shown in Table 7.
• composition of the processing solutions was as follows.
• the silver halide color photographic material prepared by using the novel yellow couplers of the present invention has the following advantageous effects.
• the yellow couplers of the present invention are not affected by a change in pH of the color developing solution and unevenness of the density of color images can be reduced.
• the yellow couplers of the present invention have high solubility in organic solvents having a high boiling point and good dispersibility and stability in a silver halide color photographic emulsion.
• the yellow couplers of the present invention have sufficient coupling activity even if the amount of organic solvents having a boiling point is reduced. Therefore, the film thickness of the light-sensitive materials can be reduced.
• a photographic light-sensitive material prepared by using the yellow couplers of the present invention can be processed at a high temperature and at a high rate of speed.

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Cited By (6)

Citations (5)

• 1985
  • 1985-12-27 JP JP60295893A patent/JPS62153954A/ja active Pending
• 1986
  • 1986-12-29 US US06/947,302 patent/US4783397A/en not_active Expired - Lifetime

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